CN1033084C - 取代的乙烯基苯的生产方法 - Google Patents
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- 238000004519 manufacturing process Methods 0.000 title claims abstract description 9
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical class C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 title claims description 10
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims abstract description 29
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 11
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims abstract 3
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims description 5
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 5
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012346 acetyl chloride Substances 0.000 claims description 4
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- 125000004432 carbon atom Chemical group C* 0.000 claims description 4
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 238000005336 cracking Methods 0.000 claims description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims description 4
- 239000001257 hydrogen Substances 0.000 claims description 4
- 239000012442 inert solvent Substances 0.000 claims description 4
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 238000000197 pyrolysis Methods 0.000 claims description 2
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical group ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims 2
- 229910000039 hydrogen halide Inorganic materials 0.000 claims 1
- 239000012433 hydrogen halide Substances 0.000 claims 1
- 239000003963 antioxidant agent Substances 0.000 abstract description 2
- 150000003440 styrenes Chemical class 0.000 abstract 2
- 230000015572 biosynthetic process Effects 0.000 abstract 1
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000013067 intermediate product Substances 0.000 abstract 1
- 238000003786 synthesis reaction Methods 0.000 abstract 1
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 15
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 9
- 238000005160 1H NMR spectroscopy Methods 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 235000019439 ethyl acetate Nutrition 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- AUFZRCJENRSRLY-UHFFFAOYSA-N 2,3,5-trimethylhydroquinone Chemical compound CC1=CC(O)=C(C)C(C)=C1O AUFZRCJENRSRLY-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical class C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 150000001299 aldehydes Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 235000007466 Corylus avellana Nutrition 0.000 description 1
- 240000003211 Corylus maxima Species 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 description 1
- GLEVLJDDWXEYCO-UHFFFAOYSA-N Trolox Chemical compound O1C(C)(C(O)=O)CCC2=C1C(C)=C(C)C(O)=C2C GLEVLJDDWXEYCO-UHFFFAOYSA-N 0.000 description 1
- 230000021736 acetylation Effects 0.000 description 1
- 238000006640 acetylation reaction Methods 0.000 description 1
- 230000003078 antioxidant effect Effects 0.000 description 1
- SYWDWCWQXBUCOP-UHFFFAOYSA-N benzene;ethene Chemical class C=C.C1=CC=CC=C1 SYWDWCWQXBUCOP-UHFFFAOYSA-N 0.000 description 1
- 150000001851 cinnamic acid derivatives Chemical class 0.000 description 1
- SUNVJLYYDZCIIK-UHFFFAOYSA-N durohydroquinone Chemical compound CC1=C(C)C(O)=C(C)C(C)=C1O SUNVJLYYDZCIIK-UHFFFAOYSA-N 0.000 description 1
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000001953 recrystallisation Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/08—1,3-Dioxanes; Hydrogenated 1,3-dioxanes condensed with carbocyclic rings or ring systems
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/18—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring
- C07C39/19—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring monocyclic with unsaturation outside the aromatic ring containing carbon-to-carbon double bonds but no carbon-to-carbon triple bonds
- C07C39/20—Hydroxy-styrenes
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C39/00—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring
- C07C39/205—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings
- C07C39/21—Compounds having at least one hydroxy or O-metal group bound to a carbon atom of a six-membered aromatic ring polycyclic, containing only six-membered aromatic rings as cyclic parts with unsaturation outside the rings with at least one hydroxy group on a non-condensed ring
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C69/00—Esters of carboxylic acids; Esters of carbonic or haloformic acids
- C07C69/017—Esters of hydroxy compounds having the esterified hydroxy group bound to a carbon atom of a six-membered aromatic ring
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- Distillation Of Fermentation Liquor, Processing Of Alcohols, Vinegar And Beer (AREA)
- Heterocyclic Compounds That Contain Two Or More Ring Oxygen Atoms (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Oxygen Or Sulfur (AREA)
- Pyrane Compounds (AREA)
- Heterocyclic Carbon Compounds Containing A Hetero Ring Having Nitrogen And Oxygen As The Only Ring Hetero Atoms (AREA)
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Abstract
本发明描述了通式
的取代乙烯基苯的新的生产方法,在此过程中三烷基对苯二酚被乙醛环合而生成乙缩醛,然后被热裂解成最终产品。
此取代的乙烯基苯是在合成抗氧化剂中有价值的中间产品。
Description
本发明涉及具有通式I的取代的乙烯基苯的新生产方法,其中R表示具有1~4个碳原子的低级烷基,R1表示氢或乙酰基,R2表示氢、1~4个碳原子的低级烷基或苄基。
取代乙烯基苯是生产抗氧化剂,比如生产Trolox CR(US-PS5080 886)的有价值的中间产品。
从《化学报告》(Chem.Berichte)1959,92,2958中可知,从三甲基对苯二酚或三甲基苯酚经过4个阶段来生产1-乙烯基-2,4,5-三甲基-3,6-二羟基苯。
在这种方法中表明,特别是最后一步,3,6二羟基-2,4,5-三甲基-肉桂酸的脱羧基化是极端困难的。
这样所得到的收率中,所希望得到的乙烯基苯仅占到加入的肉桂酸衍生物的4%。
本发明的目的是提供一种方法,它不显示这些缺点,并且有能力工业规模地生产取代乙烯苯。
本发明的目的可用如下所述的方法加以完成。
通式:
的三烷基对苯二酚,式中,R具有上述的含义,与通式III的醛,式中,R2具有上述的含义,在不含水的酸存在条件下转化成具有通式IV的乙缩醛,其中R和R′2具有上述的含义,此乙缩醛可以被乙酰氯转化成通式V的乙酰化乙缩醛,式中R和R2具有所述的含义,最后通式IV或V的乙缩醛被热解成通式的乙烯基苯,式中R、R1和R2具有上述的含义。
下面对本发明方法作更详细的描述。
较好地,三甲基对苯二酚与乙醛反应被转化成为R=CH3和R2=H的通式IV的相应乙缩醛。
反应在-30℃~30℃的温度下进行,较好地在20℃以下的温度,在惰性溶剂存在下适当地进行。
适当地过量加入乙缩醛。
加入适当的无水酸是例如:氯化氢、溴化氢、硫酸或甲磺酸。
较好用氯化氢。
从反应混合物中可用专业的方法分离生成物通式IV的乙缩醛而得到较好的收率。
通式所表示的乙缩醛至今还未被描述,故而它也是本发明的一部分。较好的通式IV的乙缩醛是R=CH3和R2=H的化合物。
所希望的是通式IV的乙缩醛被乙酰化成乙酰化乙缩醛,具有通式此式中,R和R2具有上述的含义。这种乙缩醛至今也还未被描述,所以也同样是本发明的组成部分。较好的通式V的乙酰化乙缩醛是R=CH3和R2=H的化合物。
乙酰化系在叔胺例如适当惰性溶剂中的三乙基胺存在下,用乙酰氯适当地进行。
反应在0°~100℃温度之间进行,通常实际上是定量的。
乙酰化的乙缩醛可用通常的方式从反应混和物中分离并继续进行反应。
在随后的阶段中,通式IV或V的乙缩醛被热裂解成通式I的取代乙烯基苯,其中,R、R1和R2具有所述的含义。
热裂解在300℃以上温度适当地进行,较好在400-500℃,在50Pa~10000Pa的减低压力下进行。
带R=CH3和R2=H的通式IV或V的较好乙缩醛相应地产生较好的通式I的乙烯基苯,得到R=CH3、R1=H或乙酰基和R2=H的甲基化衍生物。
R1=乙酰基的通式I的乙酰化乙烯基苯至今未被描写,因此同样也是本发明的组成部分。
相应的乙烯基苯能用这种方法以较好的收率得到,约为加入的三烷基对苯二酚的70%。
实施例1a)2,4,5,7,8-五甲基-4H-苯〔1,3〕二氧代-6-醇的生产方法
将四甲基对苯二酚(60.8g,0.4ml)悬浮于CH2Cl2(1l)中。在此悬浮液中,在不超过20℃的温度下,加入在CH2Cl2(280ml)中的乙醛(135ml,105.6g,2.4mol)溶液,然后悬浮液用气态HCl饱和,直至反应终止(用DC跟踪4∶1的甲苯/丙酮进行)。由于HCl的加入,悬浮液被逐渐溶解,将黄色的溶液于真空浓缩,得到101℃~103℃熔点的83g黄色固体(93.7%)。
1H-NMR:(C6D6,300MHz)δ以ppm表示:
5,21(q,1H,J=7Hz);
4,87(q,1H,J=6Hz);
3,78(s,1H);
2,21(s,3H);
1,94(s,3H);
1,69(s,3H);
1,52(d,3H,J=5Hz);
1,28(d,3H,J=6Hz);
同分异构体: 5,01(q,1H,J=6Hz);
4,83(q,1H,J=5Hz);
3,82(s,3H);
1,93(s,3H);
1,78(s,3H);
1,50(d,3H,J=5Hz);
1,42(d,3H,J=6Hz);b)1,4二羟基-2,3,5-三甲基-6-乙烯基苯的生产方法
将(2g,9.0mmol)2,4,5,7,8-五甲基-4H-苯〔1,3〕二氧代-6-醇于石英釜中,在460℃下并在真空(2000Pa)下热裂解,得到熔点为143℃~145℃的淡褐色固体(1g,62%)。
1H-NMR:(CDCl3,300MHz)δ以ppm表示:
6,67(dd,1H,J=12,5Hz,19Hz);
5,68(d,1H,J=12,5Hz);
5,50(d,1H,J=19Hz);
5,33(s,1H);
4,25(s,1H);
2,20(s,6H);
2,13(s,3H);实施例2.a)2,4,5,7,8-五甲基-4H苯〔1,3〕二氧代-6-基醋酸酯的生产方法
将2,4,5,7,8-五甲基-4H-苯〔1,3〕二氧代-6醇(117.4g,0.528mol)和三乙基胺(63.14g,0.624mol)在0℃CH2Cl2(80ml)中溶解。并在1小时内向此溶液中滴入乙酰氯(49.0g,0.624mol),混和物被搅拌30分钟,然后掺入水(400ml)。有机相被MgSO4干燥并真空浓缩,得到熔点为91.8℃-92.2℃的黄色固体(130.1g,93%)
1H-NMR:(CDCl3,300MHz)δ以ppm表示
5,34(q,1H,J=7,5Hz);
4,98(q,1H,J=7,5Hz);
2,35(s,3H);
2,13(s,3H);
2,04(s,3H);
1,95(s,3H);
1,54(d,3H,J=7,5Hz);
1,52(d,3H,J=7,5Hz);
同分异构体: 5,20(q,1H,J=7,5Hz);
4,96(q,1H,J=7,5Hz);
2,35(s,3H);
2,13(s,3H);
2,04(s,3H);
1,99(s,3H);
1,54(d,3H,J=7,5Hz);
1,47(d,3H,J=7,5Hz);b)4-羟基-2,5,6-三甲基-3-乙烯基苯醋酸酯的生产方法
将2,4,5,7,8-五甲基-4H苯〔1,3〕二氧代-6-基醋酸酯(20g,75.6mmol),在石英釜中,于450°并在真空(1000Pa)下热裂解。经己烷(65ml)重结晶后,得到熔点为73.5~74.8℃的白色固体(14.8g,77%)。1H-NMR:(CDCl3,400MHz)δ以ppm表示:
6,63(dd,1H,J=11,5&18,2Hz);
5,69(dd,1H,J=1,8&11,5Hz);
5,58(s,1H);
5,51(dd,1H,J=1,8&18,2Hz);
2,32(s,3H);
2,17(s,3H);
2,05(s,3H);
2,01(s,3H).
Claims (6)
1.一种具有通式的取代的乙烯基苯的生产方法,式中R表示1~4个碳原子的低级烷基,R1表示氢或乙酰基,R2表示氢、1~4个碳原子的低级烷基或苄基,其特征在于,通式的三烷基对苯二酚,式中R具有上述的含义,和通式为III的醛,式中R2具有上述的含义,在卤化氢存在下,在-30℃~30℃温度下,在惰性溶剂中进行转化至通式IV的乙缩醛式中R和R2具有上述的含义,此乙缩醛可以用乙酰氯,在叔胺存在下,在0℃~100℃的温度进行,使通式VI的乙缩醛转化成通式V的乙酰化乙缩醛,式中R和R2具有上述的含义,最后通式IV或V的乙缩醛在300℃~500℃温度之间,50Pa~10000Pa压力下被热解成通式I的乙烯基苯,式中R、R1和R2具有上述的含义。
2.如权利要求1所述的方法,其特征在于,R=CH3的三甲基衍生物用作通式II的三烷基对苯二酚,R2=H的乙醛用作通式III的醛。
3.如权利要求1所述的方法,其特征在于,氯化氢用作为向通式IV的乙缩醛转化的酸。
4.如权利要求1所述的方法,其特征在于,所用惰性溶剂为二氯甲烷。
5.如权利要求1所述的方法,其特征在于,所述的叔胺为三乙基胺。
6.如权利要求1所述的方法,其特征在于,通式IV或V的乙缩醛的热裂解系在400℃~500℃温度之间,50Pa~10000Pa的压力下进行。
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JPS61167645A (ja) * | 1985-01-22 | 1986-07-29 | Nippon Oil & Fats Co Ltd | 含フツ素芳香族誘導体の製造法 |
US5142095A (en) * | 1986-04-11 | 1992-08-25 | Warner-Lambert Company | Diarylalkanoids having activity as lipoxygenase inhibitors |
US5080886A (en) * | 1990-01-05 | 1992-01-14 | Sterling Drug Inc. | Pharmaceutical compositions for the prevention and treatment of oxidant injuries |
-
1992
- 1992-10-07 CA CA002080048A patent/CA2080048A1/en not_active Abandoned
- 1992-10-08 CN CN92111629.2A patent/CN1033084C/zh not_active Expired - Fee Related
- 1992-10-13 FI FI924622A patent/FI924622A/fi unknown
- 1992-10-20 DK DK92117942.0T patent/DK0538803T3/da active
- 1992-10-20 ES ES92117942T patent/ES2088071T3/es not_active Expired - Lifetime
- 1992-10-20 AT AT92117942T patent/ATE138903T1/de not_active IP Right Cessation
- 1992-10-20 DE DE59206483T patent/DE59206483D1/de not_active Expired - Fee Related
- 1992-10-20 JP JP4282075A patent/JPH05238975A/ja not_active Withdrawn
- 1992-10-20 EP EP92117942A patent/EP0538803B1/de not_active Expired - Lifetime
- 1992-10-21 US US07/964,056 patent/US5274176A/en not_active Expired - Fee Related
- 1992-10-22 NO NO924102A patent/NO178855C/no unknown
- 1992-10-23 IL IL103523A patent/IL103523A/xx not_active IP Right Cessation
- 1992-10-23 IL IL119561A patent/IL119561A/en not_active IP Right Cessation
-
1993
- 1993-04-08 US US08/044,168 patent/US5292748A/en not_active Expired - Fee Related
- 1993-04-08 US US08/044,166 patent/US5344963A/en not_active Expired - Fee Related
-
1996
- 1996-06-06 GR GR960401504T patent/GR3020166T3/el unknown
- 1996-11-04 IL IL11956196A patent/IL119561A0/xx unknown
Also Published As
Publication number | Publication date |
---|---|
ES2088071T3 (es) | 1996-08-01 |
IL103523A (en) | 1997-09-30 |
IL119561A0 (en) | 1997-02-18 |
US5292748A (en) | 1994-03-08 |
FI924622A0 (fi) | 1992-10-13 |
ATE138903T1 (de) | 1996-06-15 |
NO924102L (no) | 1993-04-26 |
GR3020166T3 (en) | 1996-09-30 |
US5344963A (en) | 1994-09-06 |
CA2080048A1 (en) | 1993-04-24 |
DE59206483D1 (de) | 1996-07-11 |
IL119561A (en) | 1998-02-08 |
NO178855C (no) | 1996-06-19 |
US5274176A (en) | 1993-12-28 |
JPH05238975A (ja) | 1993-09-17 |
NO178855B (no) | 1996-03-11 |
CN1071661A (zh) | 1993-05-05 |
IL103523A0 (en) | 1993-03-15 |
NO924102D0 (no) | 1992-10-22 |
EP0538803B1 (de) | 1996-06-05 |
FI924622A (fi) | 1993-04-24 |
DK0538803T3 (da) | 1996-06-24 |
EP0538803A1 (de) | 1993-04-28 |
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